WO2017077662A1 - Composition de résine photosensible, film sec et carte de circuits imprimés - Google Patents

Composition de résine photosensible, film sec et carte de circuits imprimés Download PDF

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Publication number
WO2017077662A1
WO2017077662A1 PCT/JP2016/000429 JP2016000429W WO2017077662A1 WO 2017077662 A1 WO2017077662 A1 WO 2017077662A1 JP 2016000429 W JP2016000429 W JP 2016000429W WO 2017077662 A1 WO2017077662 A1 WO 2017077662A1
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WIPO (PCT)
Prior art keywords
resin composition
photosensitive resin
carboxyl group
epoxy
group
Prior art date
Application number
PCT/JP2016/000429
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English (en)
Japanese (ja)
Inventor
倫也 樋口
橋本　壯一
貴 荒井
浩信 川里
真司 稲葉
Original Assignee
互応化学工業株式会社
新日鉄住金化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from JP2015215706A external-priority patent/JP6082083B1/ja
Priority claimed from JP2015215708A external-priority patent/JP6172816B2/ja
Priority claimed from JP2015215709A external-priority patent/JP6140246B2/ja
Application filed by 互応化学工業株式会社, 新日鉄住金化学株式会社 filed Critical 互応化学工業株式会社
Priority to KR1020167030261A priority Critical patent/KR101799845B1/ko
Priority to CN201680001165.8A priority patent/CN106796396B/zh
Publication of WO2017077662A1 publication Critical patent/WO2017077662A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • the present invention relates to a photosensitive resin composition, a dry film, and a printed wiring board, and more specifically, for forming an electrically insulating layer such as a solder resist layer, a plating resist layer, an etching resist layer, and an interlayer insulating layer on the printed wiring board.
  • the present invention relates to a photosensitive resin composition suitable for the above.
  • an electrically insulating resin composition has been used to form electrically insulating layers such as a solder resist layer, a plating resist layer, an etching resist layer, and an interlayer insulating layer of a printed wiring board.
  • a resin composition is, for example, a photosensitive resin composition.
  • Japanese Patent No. 4508929 discloses the use of a carboxyl group-containing resin having a fluorene skeleton obtained by reacting fluorene epoxy (meth) acrylate with a polyvalent carboxylic acid or an anhydride thereof.
  • the developability of a photosensitive resin composition containing a carboxyl group-containing resin having a bisphenolfluorene skeleton is low, and using such a photosensitive resin composition, an electrical insulating property such as a solder resist layer or an interlayer insulating layer can be used. It was difficult to produce a layer with a sufficient thickness by a photolithography method. In addition, even if the heat resistance of the layer formed from the above-described photosensitive resin composition can be improved, cracks are generated in such a layer while the temperature change including the temperature increase and the temperature decrease is repeated. There was a case.
  • the object of the present invention is that, even when the photosensitive resin composition contains a carboxyl group-containing resin having a bisphenolfluorene skeleton, excellent developability can be obtained, and the temperature change is repeated in the cured product.
  • Photosensitive resin composition that can hardly cause cracks, dry film that is a dried product of the photosensitive resin composition, printed wiring board including a solder resist layer containing a cured product of the photosensitive resin composition, the photosensitive resin It is providing the printed wiring board provided with the interlayer insulation layer containing the hardened
  • a photosensitive resin composition includes a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, a photopolymerization initiator ( C) and an epoxy compound (D), and the carboxyl group-containing resin (A) is represented by the following formula (1), in which R 1 to R 8 are each independently hydrogen, Reaction product of an acid anhydride and an intermediate that is a reaction product of an epoxy compound (a1) having an alkyl group having 1 to 5 carbon atoms or a halogenated bisphenolfluorene skeleton and an unsaturated group-containing carboxylic acid (a2) Containing a carboxyl group-containing resin (A1),
  • the epoxy compound (D) contains a crystalline epoxy resin and an amorphous epoxy resin, and the crystalline epoxy resin and the amorphous epoxy resin with respect to 1 equivalent of a carboxyl group contained in the carboxyl group-containing resin (A).
  • the dry film according to one embodiment of the present invention contains the photosensitive resin composition.
  • a printed wiring board according to an aspect of the present invention includes an interlayer insulating layer containing a cured product of the photosensitive resin composition.
  • a printed wiring board according to an aspect of the present invention includes a solder resist layer containing a cured product of the photosensitive resin composition.
  • FIGS. 1A to 1E are cross-sectional views illustrating steps of manufacturing a multilayer printed wiring board according to an embodiment of the present invention.
  • (meth) acryl means at least one of “acryl” and “methacryl”.
  • (meth) acrylate means at least one of acrylate and methacrylate.
  • the photosensitive resin composition according to this embodiment includes a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, and a photopolymerization initiator (C). And an epoxy compound (D).
  • the carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A1) having a bisphenolfluorene skeleton.
  • the carboxyl group-containing resin (A1) is, for example, a reaction product of an intermediate that is a reaction product of the epoxy compound (a1) and the unsaturated group-containing carboxylic acid (a2) and an acid anhydride.
  • Epoxy compound (a1) is represented by the following formula (1) wherein (1), R 1 ⁇ R 8 is independently hydrogen, alkyl or halogen having 1 to 5 carbon atoms, a bisphenol fluorene skeleton Have.
  • the carboxyl group-containing resin (A1) is synthesized by reacting the epoxy compound (a1) with the unsaturated group-containing carboxylic acid (a2), and reacting the resulting intermediate with an acid anhydride. .
  • Each of R 1 to R 8 in Formula (1) may be hydrogen, but may be an alkyl group having 1 to 5 carbon atoms or halogen. This is because even if hydrogen in the aromatic ring is substituted with a low molecular weight alkyl group or halogen, the physical properties of the carboxyl group-containing resin (A1) are not adversely affected, but rather the photosensitive resin composition containing the carboxyl group-containing resin (A1). This is because the heat resistance or flame retardancy of the cured product may be improved.
  • the carboxyl group-containing resin (A1) will be described more specifically.
  • the carboxyl group-containing resin (A1) first, at least a part of the epoxy group (see formula (2)) of the epoxy compound (a1) is reacted with the unsaturated group-containing carboxylic acid (a2).
  • the intermediate is then synthesized.
  • the intermediate has a structure (S3) represented by the following formula (3) generated by a ring-opening addition reaction between an epoxy group and an unsaturated group-containing carboxylic acid (a2). That is, the intermediate has a secondary hydroxyl group generated by a ring-opening addition reaction between an epoxy group and an unsaturated group-containing carboxylic acid (a2) in the structure (S3).
  • A is an unsaturated group-containing carboxylic acid residue.
  • carboxyl group-containing resin (A1) can be synthesized.
  • the acid anhydride may contain at least one of acid dianhydride (a3) and acid monoanhydride (a4).
  • the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton (S1) represented by the formula (1) and a structure (S4) represented by the following formula (4). And have.
  • the structure (S4) is generated by the reaction between the secondary hydroxyl group in the intermediate structure (S3) and the acid anhydride group in the acid monoanhydride (a4).
  • A is an unsaturated group-containing carboxylic acid residue
  • B is an acid monoanhydride residue.
  • the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton (S1) and a structure (S5) represented by the following formula (5).
  • Structure (S5) is generated by the reaction between two acid anhydride groups in acid dianhydride (a3) and two secondary hydroxyl groups in the intermediate. That is, the structure (S5) is generated by crosslinking the two secondary hydroxyl groups with the acid dianhydride (a3).
  • the case where two secondary hydroxyl groups present in one molecule of the intermediate are crosslinked and the case where two secondary hydroxyl groups present in each of the two molecules of the intermediate are crosslinked It is possible.
  • the two secondary hydroxyl groups present in the two molecules of the intermediate are cross-linked, the molecular weight increases.
  • A is an unsaturated group-containing carboxylic acid residue
  • D is an acid dianhydride residue.
  • a secondary hydroxyl group in the intermediate and an acid anhydride can be reacted to obtain a carboxyl group-containing resin (A1).
  • the acid anhydride contains an acid dianhydride (a3) and an acid monoanhydride (a4)
  • a part of the secondary hydroxyl group in the intermediate is reacted with the acid dianhydride (a3)
  • Another part of the secondary hydroxyl groups in the intermediate is reacted with acid monoanhydride (a4).
  • carboxyl group-containing resin (A1) can be synthesized.
  • the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton (S1), a structure (S4), and a structure (S5).
  • the carboxyl group-containing resin (A1) may further have a structure (S6) represented by the following formula (6).
  • the structure (S6) occurs when only one of the two acid anhydride groups in the acid dianhydride (a3) reacts with the secondary hydroxyl group in the intermediate.
  • A is an unsaturated group-containing carboxylic acid residue
  • D is an acid dianhydride residue.
  • the carboxyl group-containing resin (A1) has a structure (S2) represented by the formula (2), that is, an epoxy group It is possible. Further, when a part of the structure (S3) in the intermediate remains unreacted, the carboxyl group-containing resin (A1) may have the structure (S3).
  • the structure (S2) in the carboxyl group-containing resin (A1) is optimized by optimizing the reaction conditions during the synthesis of the carboxyl group-containing resin (A1).
  • the number of the structures (S6) is reduced, or the structure (S2) and the structure (S6) are almost eliminated from the carboxyl group-containing resin (A1).
  • the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton (S1), and has a structure (S4) when the acid anhydride contains acid monoanhydride (a4).
  • S1 bisphenolfluorene skeleton
  • S4 structure when the acid anhydride contains acid monoanhydride (a4).
  • the carboxyl group-containing resin (A1) may have at least one of the structure (S2) and the structure (S3).
  • carboxyl group-containing resin (A1) may have at least 1 type in a structure (S2) and a structure (S6).
  • the carboxyl group-containing resin (A1) has a structure (S2), a structure (S3), a structure ( And at least one of S6).
  • the carboxyl group-containing resin (A1) is an epoxy compound (a1). It may have a structure produced by the reaction of the secondary secondary hydroxyl group and the acid anhydride.
  • the structure of the above-mentioned carboxyl group-containing resin (A1) is reasonably inferred based on the common general technical knowledge, and the structure of the carboxyl group-containing resin (A1) cannot be specified by analysis.
  • the reason is as follows.
  • the epoxy compound (a1) itself has a secondary hydroxyl group for example, when n is 1 or more in the formula (7)
  • the carboxyl group-containing resin depends on the number of secondary hydroxyl groups in the epoxy compound (a1).
  • the structure of (A1) changes greatly.
  • the intermediate and the acid dianhydride (a3) react, as described above, two secondary hydroxyl groups present in one molecule of the intermediate are acid dianhydrides (a3).
  • the carboxyl group-containing resin (A1) finally obtained contains a plurality of molecules having different structures, and even when the carboxyl group-containing resin (A1) is analyzed, the structure cannot be specified.
  • the carboxyl group-containing resin (A1) Since the carboxyl group-containing resin (A1) has an ethylenically unsaturated group derived from the unsaturated group-containing carboxylic acid (a2), it has photoreactivity. For this reason, carboxyl group-containing resin (A1) can impart photosensitivity (specifically, ultraviolet curable) to the photosensitive resin composition. Moreover, since the carboxyl group-containing resin (A1) has a carboxyl group derived from an acid anhydride, the photosensitive resin composition contains at least one of an alkali metal salt and an alkali metal hydroxide. It is possible to impart developability with an aqueous solution.
  • the acid anhydride contains an acid dianhydride (a3)
  • the molecular weight of the carboxyl group-containing resin (A1) depends on the number of crosslinks by the acid dianhydride (a3). For this reason, the carboxyl group-containing resin (A1) in which the acid value and the molecular weight are appropriately adjusted is obtained.
  • the acid anhydride contains acid dianhydride (a3) and acid dianhydride (a4)
  • a carboxyl group-containing resin (A1) having a desired molecular weight and acid value can be easily obtained.
  • the weight average molecular weight of the carboxyl group-containing resin (A1) is preferably in the range of 1000 to 5000.
  • the weight average molecular weight is 1000 or more, tackiness of a film formed from the photosensitive resin composition is further suppressed, and insulation reliability and plating resistance of the cured product are further improved.
  • the developability by the alkaline aqueous solution of the photosensitive resin composition improves especially that a weight average molecular weight is 5000 or less.
  • the solid content acid value of the carboxyl group-containing resin (A1) is preferably in the range of 60 to 140 mgKOH / g. In this case, the developability of the photosensitive resin composition is particularly improved.
  • the solid content acid value is more preferably in the range of 80 to 135 mgKOH / g, and still more preferably in the range of 90 to 130 mgKOH / g.
  • the weight average molecular weight (Mw) of the carboxyl group-containing resin (A1) is calculated from the molecular weight measurement result by gel permeation chromatography.
  • the molecular weight measurement by gel permeation chromatography can be performed, for example, under the following conditions.
  • GPC device SHODEX SYSTEM 11, manufactured by Showa Denko KK
  • the epoxy compound (a1) has a structure (S7) represented by the following formula (7), for example.
  • N in the formula (7) is a number in the range of 0 to 20, for example.
  • the average of n is particularly preferably in the range of 0-1. If the average of n is in the range of 0 to 1, particularly when the acid anhydride contains acid dianhydride (a3), an excessive increase in molecular weight due to addition of acid dianhydride (a3) is likely to be suppressed. Become.
  • the unsaturated group-containing carboxylic acid (a2) can contain, for example, a compound having only one ethylenically unsaturated group in one molecule. More specifically, unsaturated group-containing carboxylic acid (a2) is, for example, acrylic acid, methacrylic acid, ⁇ -carboxy-polycaprolactone (n ⁇ 2) monoacrylate, crotonic acid, cinnamic acid, 2-acryloyloxyethyl succinate.
  • the reactive solution is obtained by adding the unsaturated group-containing carboxylic acid (a2) to the solvent solution of the epoxy compound (a1), further adding a thermal polymerization inhibitor and a catalyst as necessary, and stirring and mixing.
  • An intermediate can be obtained by reacting this reactive solution at a temperature of preferably 60 to 150 ° C., particularly preferably 80 to 120 ° C., by a conventional method.
  • Solvents include, for example, ketones such as methyl ethyl ketone and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene, and ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether It can contain at least one component selected from the group consisting of acetates such as acetate and dialkyl glycol ethers.
  • the thermal polymerization inhibitor contains, for example, at least one of hydroquinone and hydroquinone monomethyl ether.
  • the catalyst is at least selected from the group consisting of tertiary amines such as benzyldimethylamine and triethylamine, quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride, triphenylphosphine, and triphenylstibine.
  • tertiary amines such as benzyldimethylamine and triethylamine
  • quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride
  • triphenylphosphine triphenylstibine.
  • a kind of component can be contained.
  • the catalyst contains triphenylphosphine. That is, it is preferable to react the epoxy compound (a1) with the unsaturated group-containing carboxylic acid (a2) in the presence of triphenylphosphine. In this case, the ring-opening addition reaction between the epoxy group and the unsaturated group-containing carboxylic acid (a2) in the epoxy compound (a1) is particularly accelerated, and the reaction rate (conversion) is 95% or more, 97% or more, or almost 100%. Rate). For this reason, the intermediate body which has a structure (S3) is obtained with a high yield. Moreover, generation
  • the amount of the unsaturated group-containing carboxylic acid (a2) relative to 1 mol of the epoxy group of the epoxy compound (a1) is 0.8 to 1. It is preferably within a range of 2 moles. In this case, a photosensitive resin composition having excellent photosensitivity and storage stability can be obtained.
  • the intermediate thus obtained comprises a hydroxyl group generated by a reaction between the epoxy group of the epoxy compound (a1) and the carboxyl group of the unsaturated group-containing carboxylic acid (a2).
  • Acid dianhydride (a3) is a compound having two acid anhydride groups.
  • the acid dianhydride (a3) can contain an anhydride of tetracarboxylic acid.
  • Acid dianhydride (a3) is, for example, 1,2,4,5-benzenetetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, methylcyclohexene tetracarboxylic dianhydride, tetracarboxylic dianhydride, Naphthalene-1,4,5,8-tetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride, glycerin bisanhydrotri Melitate monoacetate, ethylene glycol bisanhydro trimellitate, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,
  • the acid dianhydride (a3) preferably contains 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride. That is, it is preferable that D in Formula (5) and Formula (6) includes a 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride residue. In this case, while ensuring good developability of the photosensitive resin composition, it is possible to further suppress the tackiness of a film formed from the photosensitive resin composition and further improve the insulation reliability and plating resistance of the cured product. .
  • the amount of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride relative to the total amount of acid dianhydride (a3) is preferably in the range of 20 to 100 mol%, and in the range of 40 to 100 mol%. Although it is more preferable to be within, it is not restricted to these ranges.
  • Acid monoanhydride (a4) is a compound having one acid anhydride group.
  • the acid monoanhydride (a4) can contain an anhydride of a dicarboxylic acid.
  • Examples of the acid monoanhydride (a4) include phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride, methylhexa Hydrophthalic anhydride, succinic anhydride, methyl succinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and It can contain at least one compound selected from the group consisting of itaconic anhydride.
  • the acid monoanhydride (a4) contains 1,2,3,6-tetrahydrophthalic anhydride. That is, the acid anhydride preferably contains 1,2,3,6-tetrahydrophthalic anhydride. That is, it is preferable that the carboxyl group-containing resin (A1) has the structure (S4), and B in the formula (4) includes a 1,2,3,6-tetrahydrophthalic anhydride residue.
  • the acid monoanhydride (a4) contains 1,2,3,6-tetrahydrophthalic anhydride. That is, the acid anhydride preferably contains 1,2,3,6-tetrahydrophthalic anhydride. That is, it is preferable that the carboxyl group-containing resin (A1) has the structure (S4), and B in the formula (4) includes a 1,2,3,6-tetrahydrophthalic anhydride residue.
  • the amount of 1,2,3,6-tetrahydrophthalic anhydride relative to the entire acid monoanhydride (a4) is preferably in the range of 20 to 100 mol%, and in the range of 40 to 100 mol%. Is more preferable, but is not limited to these ranges.
  • a known method can be employed. For example, an acid anhydride is added to the solvent solution of the intermediate, and a thermal polymerization inhibitor and a catalyst are further added as necessary, followed by stirring and mixing to obtain a reactive solution. By reacting this reactive solution at a temperature of preferably 60 to 150 ° C., particularly preferably 80 to 120 ° C., a carboxyl group-containing resin (A1) can be obtained by a conventional method.
  • a solvent, catalyst and polymerization inhibitor appropriate ones can be used, and the solvent, catalyst and polymerization inhibitor used in the synthesis of the intermediate can also be used as they are.
  • the catalyst contains triphenylphosphine. That is, it is preferable to react an intermediate with an acid anhydride in the presence of triphenylphosphine. In this case, the reaction between the secondary hydroxyl group and the acid anhydride in the intermediate is particularly accelerated, and a reaction rate (conversion rate) of 90%, 95%, 97%, or almost 100% can be achieved. For this reason, the carboxyl group-containing resin (A1) having at least one of the structure (S4) and the structure (S5) is obtained in a high yield. Moreover, generation
  • the amount of the acid dianhydride (a3) is 1 mol of the epoxy group of the epoxy compound (a1), A range of 0.05 to 0.24 mol is preferred.
  • the amount of acid monoanhydride (a4) is preferably in the range of 0.3 to 0.7 mol with respect to 1 mol of the epoxy group of the epoxy compound (a1). In this case, the carboxyl group-containing resin (A1) in which the acid value and the molecular weight are appropriately adjusted can be easily obtained.
  • the carboxyl group-containing resin (A) may contain only the carboxyl group-containing resin (A1), or a carboxyl group-containing resin other than the carboxyl group-containing resin (A1) (hereinafter also referred to as carboxyl group-containing resin (F)). May further be contained.
  • the carboxyl group-containing resin (F) can contain, for example, a compound having a carboxyl group and not having photopolymerizability (hereinafter referred to as (F1) component).
  • (F1) A component contains the polymer of the ethylenically unsaturated monomer containing the ethylenically unsaturated compound which has a carboxyl group, for example.
  • the ethylenically unsaturated compound having a carboxyl group can contain compounds such as acrylic acid, methacrylic acid, and ⁇ -carboxy-polycaprolactone (n ⁇ 2) monoacrylate.
  • the ethylenically unsaturated compound having a carboxyl group can also contain a reaction product of pentaerythritol triacrylate, pentaerythritol trimethacrylate and the like with a dibasic acid anhydride.
  • Ethylenically unsaturated monomers include 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, linear or branched aliphatic or alicyclic (provided that It may further contain an ethylenically unsaturated compound having no carboxyl group, such as (meth) acrylic acid ester (which may partially have an unsaturated bond in the ring).
  • the carboxyl group-containing resin (F) may contain a compound having a carboxyl group and an ethylenically unsaturated group (hereinafter referred to as (F2) component). Moreover, carboxyl group-containing resin (F) may contain only the (F2) component.
  • the component (F2) includes, for example, an intermediate that is a reaction product of an epoxy compound (g1) having two or more epoxy groups in one molecule and an ethylenically unsaturated compound (g2), a polyvalent carboxylic acid and its anhydride.
  • a resin (referred to as a first resin (g)) that is a reaction product with at least one compound (g3) selected from the group of substances.
  • the first resin (g) is obtained by adding the compound (g3) to an intermediate obtained by reacting the epoxy group in the epoxy compound (g1) with the carboxyl group in the ethylenically unsaturated compound (g2).
  • the epoxy compound (g1) can contain an appropriate epoxy resin such as a cresol novolac epoxy resin or a phenol novolac epoxy resin.
  • the epoxy compound (g1) may contain a polymer of the ethylenically unsaturated compound (h).
  • the ethylenically unsaturated compound (h) contains a compound (h1) having an epoxy group such as glycidyl (meth) acrylate, or further has no epoxy group such as 2- (meth) acryloyloxyethyl phthalate.
  • the ethylenically unsaturated compound (g2) preferably contains at least one of acrylic acid and methacrylic acid.
  • the compound (g3) contains one or more compounds selected from the group consisting of polyvalent carboxylic acids such as phthalic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid, and anhydrides of these polyvalent carboxylic acids. .
  • the component (F2) is a resin (second resin) that is a reaction product of a polymer of an ethylenically unsaturated monomer containing an ethylenically unsaturated compound having a carboxyl group and an ethylenically unsaturated compound having an epoxy group. (I)) may be contained.
  • the ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group.
  • the second resin (i) can be obtained by reacting an ethylenically unsaturated compound having an epoxy group with a part of the carboxyl group in the polymer.
  • the ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group.
  • the ethylenically unsaturated compound having a carboxyl group include compounds such as acrylic acid, methacrylic acid, ⁇ -carboxy-polycaprolactone (n ⁇ 2) monoacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate.
  • Examples of the ethylenically unsaturated compound having no carboxyl group include 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, linear or branched aliphatic or fatty acid It contains a compound such as a (meth) acrylic acid ester of a cyclic group (however, it may have a partially unsaturated bond in the ring).
  • the ethylenically unsaturated compound having an epoxy group preferably contains glycidyl (meth) acrylate.
  • the carboxyl group-containing resin (A) contains only the carboxyl group-containing resin (A1) or the carboxyl group-containing resin (A1) and the carboxyl group-containing resin (F).
  • the carboxyl group-containing resin (A) preferably contains 30% by mass or more of the carboxyl group-containing resin (A1), more preferably 50% by mass or more, and still more preferably 100% by mass.
  • the heat resistance and insulation reliability of the cured product of the photosensitive resin composition can be particularly improved.
  • membrane formed from the photosensitive resin composition can fully be reduced.
  • the developability of the photosensitive resin composition with an alkaline aqueous solution can be secured.
  • the photosensitive resin composition includes a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, and a photopolymerization initiator (C). And an epoxy compound (D).
  • the unsaturated compound (B) can impart photocurability to the photosensitive resin composition.
  • the unsaturated compound (B) is, for example, a monofunctional (meth) acrylate such as 2-hydroxyethyl (meth) acrylate; and diethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ⁇ -caprolactone modified pentaerythritol hexaacrylate, tricyclodecandi
  • At least one compound selected from the group consisting of polyfunctional (meth) acrylates such as methanol di (meth) acrylate
  • the unsaturated compound (B) preferably contains a trifunctional compound, that is, a compound having three unsaturated bonds in one molecule.
  • a trifunctional compound that is, a compound having three unsaturated bonds in one molecule.
  • Trifunctional compounds include, for example, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate and ⁇ -caprolactone modified It can contain at least one compound selected from the group consisting of tris- (2-acryloxyethyl) isocyanurate and ethoxylated glycerin tri (meth) acrylate.
  • the unsaturated compound (B) contains a phosphorus-containing compound (phosphorus-containing unsaturated compound).
  • Phosphorus-containing unsaturated compounds include, for example, 2-methacryloyloxyethyl acid phosphate (specific examples: product number light ester P-1M and light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.), 2-acryloyloxyethyl acid phosphate (Specific examples are product number light acrylate P-1A manufactured by Kyoeisha Chemical Co., Ltd.), diphenyl-2-methacryloyloxyethyl phosphate (specific examples are product number MR-260 manufactured by Daihachi Industry Co., Ltd.), and Showa Polymer Co., Ltd.
  • HFA series (part number HFA-6003, which is an addition reaction product of dipentaerystol hexaacrylate and HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) as a specific example, and HFA-6007, caprolactone Product No. HFA-3003, HFA-6127, etc., which are addition reaction products of modified dipentaerystol hexaacrylate and HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) It can contain at least one compound selected from the group.
  • the unsaturated compound (B) may contain a prepolymer.
  • the prepolymer is at least one selected from the group consisting of, for example, a prepolymer obtained by polymerizing a monomer having an ethylenically unsaturated bond and then adding an ethylenically unsaturated group, and oligo (meth) acrylate prepolymers These compounds can be contained.
  • Oligo (meth) acrylate prepolymers include, for example, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate At least one component selected from the group consisting of:
  • the photopolymerization initiator (C) contains, for example, an acyl phosphine oxide photopolymerization initiator (C1). That is, the photosensitive resin composition contains, for example, an acyl phosphine oxide photopolymerization initiator (C1).
  • the photosensitive resin composition contains the carboxyl group-containing resin (A1), high sensitivity to ultraviolet rays can be imparted to the photosensitive resin composition.
  • cured material of the photosensitive resin composition is suppressed, and the insulation reliability of the same layer improves further.
  • the acylphosphine oxide photopolymerization initiator (C1) is unlikely to hinder the electrical insulation of the cured product. For this reason, by curing the photosensitive resin composition by exposure, a cured product having excellent electrical insulation can be obtained.
  • This cured product can be used as, for example, a solder resist layer, a plating resist layer, an etching resist layer, or an interlayer insulating layer. Is preferred.
  • Acylphosphine oxide photopolymerization initiators (C1) include monoacyl such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4,6-trimethylbenzoyl-ethyl-phenyl-phosphinate, etc.
  • Phosphine oxide photopolymerization initiator and bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2 , 6-Dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybe Zoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzoyl) phenylphosphine Contains at least one component selected from the group consist
  • the acylphosphine oxide photopolymerization initiator (C1) preferably contains 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and the acylphosphine oxide photopolymerization initiator (C1) contains 2, It is also preferred to contain only 4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • the photopolymerization initiator (C) preferably contains a hydroxyketone photopolymerization initiator (C2) in addition to the acylphosphine oxide photopolymerization initiator (C1). That is, the photosensitive resin composition preferably contains a hydroxyketone photopolymerization initiator (C2). In this case, higher photosensitivity can be imparted to the photosensitive resin composition as compared with the case where the hydroxyketone photopolymerization initiator (C2) is not contained. Thereby, when irradiating and hardening an ultraviolet-ray to the coating film formed from the photosensitive resin composition, it becomes possible to fully harden a coating film over the deep part from the surface.
  • Examples of the hydroxyketone photopolymerization initiator (C2) include 1-hydroxy-cyclohexyl-phenyl-ketone, phenylglyoxyc acid methyl ester, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy -2-Methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propane-1- On and 2-hydroxy-2-methyl-1-phenyl-propan-1-one.
  • the mass ratio of the acylphosphine oxide photopolymerization initiator (C1) and the hydroxyketone photopolymerization initiator (C2) is preferably in the range of 1: 0.01 to 1:10. In this case, the curability in the vicinity of the surface of the coating film formed from the photosensitive resin composition and the curability in the deep portion can be improved in a well-balanced manner.
  • the photopolymerization initiator (C) preferably contains bis (diethylamino) benzophenone (C3). That is, the photosensitive resin composition contains an acyl phosphine oxide photopolymerization initiator (C1) and bis (diethylamino) benzophenone (C3), or an acyl phosphine oxide photopolymerization initiator (C1), a hydroxyketone type. It is also preferable to contain a photopolymerization initiator (C2) and bis (diethylamino) benzophenone (C3). In this case, when developing after partially exposing the coating film formed from the photosensitive resin composition, since the hardening of the part which is not exposed is suppressed, resolution becomes especially high.
  • cured material of the photosensitive resin composition of a very fine pattern can be formed.
  • an interlayer insulating layer of a multilayer printed wiring board is prepared from a photosensitive resin composition and a small-diameter hole for a through hole is provided in the interlayer insulating layer by a photolithography method (see FIG. 1), the small-diameter hole is formed. Precise and easy to form.
  • the amount of bis (diethylamino) benzophenone (C3) relative to the acylphosphine oxide photopolymerization initiator (C1) is preferably in the range of 0.5 to 20% by mass.
  • the amount of bis (diethylamino) benzophenone (C3) with respect to the acylphosphine oxide photopolymerization initiator (C1) is 0.5% by mass or more, the resolution is particularly high.
  • the amount of bis (diethylamino) benzophenone (C3) relative to the acylphosphine oxide-based photopolymerization initiator (C1) is 20% by mass or less, the electrical insulation of the cured product of the photosensitive resin composition is increased to bis (diethylamino). ) Benzophenone (C3) is difficult to inhibit.
  • the photosensitive resin composition may further contain a known photopolymerization accelerator, sensitizer and the like.
  • the photosensitive resin composition includes benzoin and its alkyl ethers; acetophenones such as acetophenone and benzyldimethyl ketal; anthraquinones such as 2-methylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2- Thioxanthones such as isopropylthioxanthone, 4-isopropylthioxanthone and 2,4-diisopropylthioxanthone; benzophenones such as benzophenone and 4-benzoyl-4′-methyldiphenyl sulfide; xanthones such as 2,4-diisopropylxanthone; ⁇ -hydroxyketones such as hydroxy-2-methyl-1-phenyl-propan-1-one; 2-methyl-1- [4-
  • the photosensitive resin composition includes known photopolymerization initiators (C) and tertiary amines such as p-dimethylbenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and 2-dimethylaminoethylbenzoate. You may contain a photoinitiator, a sensitizer, etc.
  • the photosensitive resin composition may contain at least one of a photopolymerization initiator for visible light exposure and a photopolymerization initiator for near infrared exposure, if necessary.
  • the photosensitive resin composition contains a photopolymerization initiator (C) and a coumarin derivative such as 7-diethylamino-4-methylcoumarin, which is a sensitizer for laser exposure, a carbocyanine dye system, a xanthene dye system, and the like. May be.
  • the epoxy compound (D) can impart thermosetting properties to the photosensitive resin composition.
  • the epoxy compound (D) contains a crystalline epoxy resin and an amorphous epoxy resin.
  • the “crystalline epoxy resin” is an epoxy resin having a melting point
  • the “amorphous epoxy resin” is an epoxy resin having no melting point.
  • Examples of crystalline epoxy resins include 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, hydroquinone type crystals Epoxy resin (specifically, product name YDC-1312 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), biphenyl type crystalline epoxy resin (specifically, product name YX-4000 manufactured by Mitsubishi Chemical Corporation), diphenyl ether type crystalline epoxy resin (specifically For example, Nippon Steel & Sumikin Chemical Co., Ltd., product number YSLV-80DE), bisphenol type crystalline epoxy resin (specifically, Nippon Steel & Sumikin Chemical Co., Ltd.
  • product name YSLV-80XY tetrakisphenol ethane type crystalline epoxy resin (specific example) Nippon Kayaku Co., Ltd. product number GTR-1800), bisphenolfluorene type
  • the crystalline epoxy resin preferably has two epoxy groups in one molecule. In this case, it is possible to further prevent cracks in the cured product while the temperature change is repeated.
  • the crystalline epoxy resin preferably has an epoxy equivalent of 150 to 300 g / eq. This epoxy equivalent is the gram weight of a crystalline epoxy resin containing 1 gram equivalent of epoxy groups.
  • the crystalline epoxy resin has a melting point. Examples of the melting point of the crystalline epoxy resin include 70 to 180 ° C.
  • the epoxy compound (D) preferably contains a crystalline epoxy resin having a melting point of 110 ° C. or lower.
  • the developability of the photosensitive resin composition with an alkaline aqueous solution is particularly improved.
  • biphenyl type epoxy resins specifically, product number YX-4000 manufactured by Mitsubishi Chemical Corporation
  • biphenyl ether type epoxy resins specifically, product number YSLV manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • a bisphenol-type epoxy resin specifically, product number YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical
  • a bisphenolfluorene-type crystalline epoxy resin specifically, an epoxy resin having the structure (S7). At least one component.
  • Amorphous epoxy resins include, for example, phenol novolac type epoxy resins (specifically, product number EPICLON N-775 manufactured by DIC Corporation) and cresol novolac type epoxy resins (specific examples, product number EPICLON N-695 manufactured by DIC Corporation).
  • Bisphenol A novolac type epoxy resin (specific example, product number EPICLON N-865 manufactured by DIC Corporation), bisphenol A type epoxy resin (specific example, product number jER1001 manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (specific example As product number jER4004P manufactured by Mitsubishi Chemical Co., Ltd.), bisphenol S type epoxy resin (specifically, product number EPICLON EXA-1514 manufactured by DIC Corporation), bisphenol AD type epoxy resin, biphenyl novolac Type epoxy resin (part number NC-3000 manufactured by Nippon Kayaku Co., Ltd.), hydrogenated bisphenol A type epoxy resin (part number ST-4000D manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), naphthalene type epoxy resin (particular Examples include DIC Corporation part numbers EPICLON HP-4032, EPICLON HP-4700, EPICLON HP-4770), tertiary butyl catechol type epoxy resin (specific examples DIC Corporation part number EPICLON HP-820), dicyclopentad
  • Type epoxy resin (specifically, product number EPICLON HP-7200 manufactured by DIC), adamantane type epoxy resin (specific example, product number ADAMANTATE X-E-201 manufactured by Idemitsu Kosan Co., Ltd.), special bifunctional epoxy resin (tool)
  • product numbers YL7175-500 and YL7175-1000 manufactured by Mitsubishi Chemical Corporation product numbers EPICLON TSR-960, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON 1650-75MPX, EPICLON EXA- manufactured by DIC Corporation 4850, EPICLON EXA-4816, EPICLON EXA-4822, and EPICLON EXA-9726
  • product number YSLV-120TE manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. rubber core-shell polymer modified bisphenol A type epoxy resin (specifically, manufactured by Kaneka Corporation) Product number MX-156), rubber-like core-shell polymer modified
  • the epoxy compound (D) may contain a phosphorus-containing epoxy resin.
  • the phosphorus-containing epoxy resin may be contained in the crystalline epoxy resin or may be contained in the amorphous epoxy resin.
  • Examples of the phosphorus-containing epoxy resin include phosphoric acid-modified bisphenol F type epoxy resin (specific examples, product numbers EPICLON EXA-9726 and EPICLON EXA-9710 manufactured by DIC Corporation), and product number Epototo FX-305 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Etc.
  • the amorphous epoxy resin preferably contains an epoxy resin (da) having a bisphenol type structural unit (d1) and a structural unit (d2).
  • an epoxy resin (da) having a bisphenol type structural unit (d1) and a structural unit (d2).
  • the thermal shock resistance of the cured product of the photosensitive resin composition can be improved.
  • Examples of the structural unit (d1) include structural units derived from bisphenol A, bisphenol F, and bisphenol S. Specific examples of the structural unit (d1) include units excluding these terminal OH groups and units represented by the following formula (8). Moreover, a part of phenylene group and phenyl group in the unit represented by the formula (8) may be hydrogenated. Furthermore, the phenylene group and the phenyl group in the unit represented by the formula (8) may have a substituent such as a hydrocarbon group, an alkoxyl group, an aryl group, an aryloxy group, or a hydroxyl group.
  • the structural unit (d2) is selected from the group consisting of a linear hydrocarbon structural unit (d21) having 4 to 20 carbon atoms and a polyalkylene ether structural unit (d22) having 3 to 20 ether oxygen atoms. It consists of at least one kind.
  • the linear hydrocarbon structural unit (d21) is a structural unit in which y of — (CH 2 ) y — is 4 or more and 20 or less. y is preferably 4 to 10. Note that a substituent such as a hydroxyl group may be substituted for a hydrogen atom in a structural unit in which y of — (CH 2 ) y — is 4 or more and 20 or less. Furthermore, - (CH 2) y- y although at least one hydrogen atom in the structural unit is 4 or more 20 or less, a hydrocarbon group, an alkoxyl group, an aryl group, may be substituted with an aryloxy group .
  • the hydrocarbon and alkoxyl groups as the substituent preferably have 4 or less carbon atoms.
  • the aryl group in the aryl group and aryloxy group is preferably a phenyl group.
  • the linear hydrocarbon structural unit (d21) may have these substituents as long as the flexibility of the structural unit (d2) is not impaired
  • the number of ether oxygen atoms is 3 or more and 20 or less, preferably 3 to 10.
  • the polyalkylene ether structural unit (d22) is derived from a polymer of one or more alkylene oxides selected from ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, neopentylene oxide, tetramethylene oxide, and the like. These structural units are exemplified.
  • One or more hydrogen atoms of the alkylene oxide may be substituted with, for example, a hydroxyl group, an alkoxyl group, an aryl group, an aryloxy group, a hydrocarbon group, or the like.
  • the hydrocarbon and alkoxyl groups as the substituent preferably have 4 or less carbon atoms.
  • the aryl group in the aryl group and aryloxy group is preferably a phenyl group.
  • the polyalkylene ether structural unit (d22) may have these substituents as long as the flexibility of the structural unit (d2) is not impaired.
  • the molar ratio of the structural unit (d1) to the structural unit (d2) is preferably 10: 1 to 1: 5, and more preferably 5: 1 to 1: 3.
  • the amorphous epoxy resin does not have sufficient flexibility and the cured product of the photosensitive resin composition may be easily cracked.
  • the Tg of the amorphous epoxy resin is too low, and the heat resistance of the cured product of the photosensitive resin composition may be reduced.
  • the epoxy resin (da) preferably has one or more structures represented by the following structural formulas (9-i) to (9-iv). Further, a plurality of hydroxyl groups in the structural formula shown below may undergo a crosslinking reaction, and the oxygen atom of the hydroxyl group may knot an unspecified structure.
  • Ar 1 and Ar 2 are hydrogenated or may have a substituent (d1). Ar 1 and Ar 2 may be the same or different.
  • X is at least one selected from the group consisting of a linear hydrocarbon group having 4 to 20 carbon atoms and a polyalkylene ether structure having 1 to 18 ether oxygen atoms. When X is a linear hydrocarbon group having 4 to 20 carbon atoms, X constitutes the structural unit (d2). In the case where X is a polyalkylene ether structure having 1 to 18 ether oxygen atoms, —O—X—O— constitutes the structural unit (d2). N is an average value of repeating units and is 1 to 30.
  • this predetermined epoxy resin a method using an epoxy compound having structural units (d1) and (d2) as described above; an epoxy compound having structural unit (d1) and an epoxy compound having structural unit (d2) And an epoxy compound having the structural unit (d1) and a chain extender that can impart the structural unit (d2) to the epoxy compound by a reaction.
  • epoxy compound (da) examples include product numbers EPICLON EXA4816 and EPICLON EXA4822 manufactured by DIC Corporation, and product numbers YL7175-500 and YL7175-1000 manufactured by Mitsubishi Chemical Corporation.
  • the epoxy equivalent of the epoxy compound having the structural unit (d1) and the structural unit (d2) is preferably 200 to 800 g / eq, and more preferably 350 to 650 g / eq.
  • the amorphous epoxy resin preferably contains an epoxy resin (db) having a novolak structure and a biphenyl skeleton.
  • the photosensitive resin composition containing the epoxy resin (db) has high electrical insulation performance of the cured product. For this reason, the photosensitive resin composition is particularly suitable as an insulating material for a printed wiring board that requires high reliability such as line insulation and interlayer migration resistance.
  • the epoxy resin (db) is an amorphous biphenyl novolac type epoxy resin (specific examples: product number NC-3000, product number NC-3000-L, product number NC-3000-H, product number NC-3000 manufactured by Nippon Kayaku Co., Ltd.) -FH-75M, CER-3000-L) and the like.
  • the photosensitive resin composition according to the present embodiment may contain melamine (E).
  • E melamine
  • the adhesion between the cured product of the photosensitive resin composition and a metal such as copper is increased.
  • the photosensitive resin composition is particularly suitable as an insulating material for a printed wiring board.
  • the plating resistance of the cured product of the photosensitive resin composition that is, the whitening resistance during the electroless nickel / gold plating process is improved.
  • the photosensitive resin composition according to this embodiment may contain an organic solvent.
  • the organic solvent is used for the purpose of liquefaction or varnishing of the photosensitive resin composition, viscosity adjustment, application property adjustment, film formation property adjustment, and the like.
  • Organic solvents include, for example, linear, branched, secondary or polyhydric alcohols such as ethanol, propyl alcohol, isopropyl alcohol, hexanol and ethylene glycol; ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene Petroleum aromatic mixed solvents such as Swazol series (manufactured by Maruzen Petrochemical Co., Ltd.), Solvesso series (manufactured by Exxon Chemical Co., Ltd.), cellosolves such as cellosolve and butylcellosolve, and carbitols such as carbitol and butylcarbitol Tolls; propylene glycol alkyl ethers such as propylene glycol methyl ether; polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; ethyl acetate, butyl acetate, cellosolve acetate
  • the amount of the component in the photosensitive resin composition is appropriately adjusted so that the photosensitive resin composition has photocurability and can be developed with an alkaline solution.
  • the amount of the carboxyl group-containing resin (A) relative to the solid content of the photosensitive resin composition is preferably within the range of 5 to 85% by mass, more preferably within the range of 10 to 75% by mass, and 30 to 60%. If it is in the range of mass%, it is still more preferable.
  • the amount of the unsaturated compound (B) relative to the carboxyl group-containing resin (A) is preferably in the range of 1 to 50% by mass, more preferably in the range of 10 to 45% by mass, and 21 to 40% by mass. If it is in the range, it is more preferable.
  • the amount of the photopolymerization initiator (C) relative to the carboxyl group-containing resin (A) is preferably in the range of 0.1 to 30% by mass, and more preferably in the range of 1 to 25% by mass.
  • the total of the equivalents of epoxy groups contained in the epoxy compound (D) is 0.7 to 2.5 with respect to 1 equivalent of carboxyl groups contained in the carboxyl group-containing resin (A). Is preferably in the range of 0.7 to 2.3, more preferably in the range of 0.7 to 2.0.
  • the total of the equivalents of the epoxy groups contained in the crystalline epoxy resin and the amorphous epoxy resin with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A) is 2.5 or less, so that developability is improved. Can be improved. More preferably, the total of the equivalents of the epoxy groups contained in the crystalline epoxy resin and the amorphous epoxy resin with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A) is 0.7 to 2.3. 0.7 to 2.0 is more preferable.
  • the equivalent of the epoxy group of the crystalline epoxy resin to one equivalent of the carboxyl group contained in the carboxyl group-containing resin (A) is preferably in the range of 0.2 to 1.9. In this case, the developability of the photosensitive resin composition can be particularly improved.
  • the equivalent of the epoxy group of the crystalline epoxy resin to one equivalent of the carboxyl group contained in the carboxyl group-containing resin (A) is more preferably within the range of 0.3 to 1.7.
  • the equivalent of the epoxy group contained in the amorphous epoxy resin with respect to one equivalent of the carboxyl group contained in the carboxyl group-containing resin (A) is preferably in the range of 0.05 to 1.5. In this case, the developability of the photosensitive resin composition can be improved, and the crack resistance of the cured product can be particularly improved while the temperature change is repeated.
  • the equivalent of the epoxy group contained in the amorphous epoxy resin with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A) is more preferably 0.1 to 1.2.
  • the amount of melamine (E) with respect to the carboxyl group-containing resin (A) is preferably in the range of 0.1 to 10% by mass, More preferably, it is in the range of ⁇ 5% by mass.
  • the amount of the organic solvent is such that when the coating film formed from the photosensitive resin composition is dried, the organic solvent is quickly volatilized and eliminated, that is, the organic solvent. Is preferably adjusted so as not to remain in the dry film.
  • the amount of the organic solvent relative to the entire photosensitive resin composition is preferably in the range of 0 to 99.5% by mass, and more preferably in the range of 15 to 60% by mass.
  • the suitable ratio of an organic solvent changes with application methods etc., it is preferable to adjust a ratio suitably according to the application method.
  • solid content is a total amount of all the components remove
  • the photosensitive resin composition may further contain components other than the above components.
  • the photosensitive resin composition may contain an inorganic filler.
  • the inorganic filler can contain, for example, one or more materials selected from the group consisting of barium sulfate, crystalline silica, nano silica, carbon nanotubes, talc, bentonite, aluminum hydroxide, magnesium hydroxide, and titanium oxide. You may whiten the photosensitive resin composition and its hardened
  • the proportion of the inorganic filler in the photosensitive resin composition is appropriately set, but the amount of the inorganic filler with respect to the carboxyl group-containing resin (A) is preferably in the range of 0 to 300% by mass.
  • Photosensitive resin composition comprising tolylene diisocyanate, morpholine diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate blocked isocyanates blocked with caprolactam, oxime, malonic acid ester, etc .; melamine resin, n-butylated melamine resin , Amino resins such as isobutylated melamine resin, butylated urea resin, butylated melamine urea cocondensation resin, benzoguanamine cocondensation resin; various other thermosetting resins; ultraviolet curable epoxy (meth) acrylate; bisphenol A type , Phenol novolak type, cresol novolak type, alicyclic type and other epoxy resins obtained by adding (meth) acrylic acid; and diallyl phthalate resin, phenoxy resin, urethane resin, fluorine resin At least one resin selected from the group consisting of polymer compounds may be contained.
  • the photosensitive resin composition may contain a curing agent for curing the epoxy compound (D).
  • the curing agent include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2 Imidazole derivatives such as -cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, Amine compounds such as 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic hydrazide and sebacic acid hydrazide; phosphorus compounds such as triphenylphosphine; acid anhydr
  • the photosensitive resin composition may contain an adhesion-imparting agent other than melamine (E).
  • adhesion-imparting agent include guanamine, acetoguanamine, benzoguanamine, and 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl- S-triazine derivatives such as 4,6-diamino-S-triazine / isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct.
  • Photosensitive resin composition includes curing accelerator; colorant; copolymer such as silicone and acrylate; leveling agent; adhesion imparting agent such as silane coupling agent; thixotropic agent; polymerization inhibitor; antihalation agent; An antifoaming agent; an antioxidant; a surfactant; and at least one component selected from the group consisting of polymer dispersants.
  • the content of the amine compound in the photosensitive resin composition is preferably as small as possible. If it does in this way, the electrical insulation of the layer which consists of hardened
  • the amount of the amine compound relative to the carboxyl group-containing resin (A) is preferably 6% by mass or less, and more preferably 4% by mass or less.
  • the photosensitive resin composition can be prepared by blending the raw materials of the photosensitive resin composition as described above and kneading by a known kneading method using, for example, a three-roll, ball mill, sand mill or the like.
  • the raw material of the photosensitive resin composition contains a liquid component, a low viscosity component, etc.
  • the part of the raw material excluding the liquid component, the low viscosity component, etc. is first kneaded, and the resulting mixture is
  • the photosensitive resin composition may be prepared by adding and mixing a liquid component, a component having a low viscosity, and the like.
  • the first agent may be prepared by mixing a part of the components of the photosensitive resin composition
  • the second agent may be prepared by mixing the rest of the components.
  • the photosensitive resin composition may include a first agent and a second agent.
  • the first agent is prepared by previously mixing and dispersing the unsaturated compound (B), a part of the organic solvent, and the thermosetting component among the components of the photosensitive resin composition.
  • You may prepare a 2nd agent by mixing and disperse
  • the photosensitive resin composition according to this embodiment is suitable for an electrically insulating material for a printed wiring board.
  • the photosensitive resin composition is suitable for materials for electrically insulating layers such as a solder resist layer, a plating resist layer, an etching resist layer, and an interlayer insulating layer.
  • the photosensitive resin composition according to the present embodiment preferably has such a property that even a 25 ⁇ m thick film can be developed with an aqueous sodium carbonate solution.
  • the photosensitive resin composition since it is possible to produce a sufficiently thick electrically insulating layer from the photosensitive resin composition by a photolithography method, the photosensitive resin composition is used as an interlayer insulating layer, a solder resist layer, etc. in a printed wiring board. It can be widely applied to fabricate. Of course, it is also possible to produce an electrically insulating layer having a thickness of less than 25 ⁇ m from the photosensitive resin composition.
  • a wet paint film is formed by applying the photosensitive resin composition on a suitable substrate, and this wet paint film is heated at 80 ° C. for 40 minutes to form a film having a thickness of 25 ⁇ m.
  • the film is exposed by irradiating the film with ultraviolet light under the condition of 500 mJ / cm 2 with a negative mask having an exposed part that transmits ultraviolet light and a non-exposed part that blocks ultraviolet light directly applied. After the exposure, a 1% Na 2 CO 3 aqueous solution at 30 ° C.
  • the film having a thickness of 25 ⁇ m can be developed with an aqueous sodium carbonate solution when a portion corresponding to the non-exposed portion of the film is removed and no residue is observed.
  • FIGS. 1A to 1E an example of a method for producing a printed wiring board including an interlayer insulating layer formed from the photosensitive resin composition according to the present embodiment will be described with reference to FIGS. 1A to 1E.
  • a through hole is formed in the interlayer insulating layer by photolithography.
  • a core material 1 is prepared as shown in FIG. 1A.
  • the core material 1 includes, for example, at least one insulating layer 2 and at least one conductor wiring 3.
  • the conductor wiring 3 provided on one surface of the core material 1 is hereinafter referred to as a first conductor wiring 3.
  • a film 4 is formed on one surface of the core material 1 from a photosensitive resin composition. Examples of the method for forming the film 4 include a coating method and a dry film method.
  • a photosensitive resin composition is applied on the core material 1 to form a wet paint film.
  • the method for applying the photosensitive resin composition is selected from the group consisting of known methods such as dipping, spraying, spin coating, roll coating, curtain coating, and screen printing.
  • the wet coating film is dried at a temperature in the range of 60 to 120 ° C., for example, whereby the coating film 4 can be obtained.
  • a photosensitive resin composition is first applied on an appropriate support made of polyester or the like and then dried to form a dry film that is a dried product of the photosensitive resin composition on the support. To do. Thereby, a laminated body provided with a dry film and the support body which supports a dry film is obtained. After the dry film in this laminate is overlaid on the core material 1, pressure is applied to the dry film and the core material 1, and then the support is peeled from the dry film, so that the dry film is placed on the core material 1 from the support. Transfer to Thereby, the coating 4 made of a dry film is provided on the core material 1.
  • the coating 4 is partially cured by exposing the coating 4 as shown in FIG. 1C.
  • a negative mask is applied to the film 4 and then the film 4 is irradiated with ultraviolet rays.
  • the negative mask includes an exposure part that transmits ultraviolet light and a non-exposure part that blocks ultraviolet light, and the non-exposure part is provided at a position that matches the position of the through hole 10.
  • the negative mask is a photo tool such as a mask film or a dry plate.
  • the ultraviolet light source is selected from the group consisting of chemical lamps, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and metal halide lamps, for example.
  • the exposure method may be a method other than a method using a negative mask.
  • the film 4 may be exposed by a direct drawing method in which only the portion of the film 4 to be exposed is irradiated with ultraviolet rays emitted from a light source.
  • the light source applied to the direct drawing method is, for example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, g-line (436 nm), h-line (405 nm), i-line (365 nm), and g-line, h-line, and i-line. It is selected from the group consisting of two or more kinds of combinations.
  • the film 4 is exposed by irradiating the film 4 made of the dry film with ultraviolet rays through the support without peeling the support after the dry film in the laminate is stacked on the core material 1. Subsequently, the support may be peeled off from the film 4 before development processing.
  • the coating 4 is developed to remove the unexposed portion 5 of the coating 4 shown in FIG. 1C, whereby the hole 6 is formed at the position where the through hole 10 is formed as shown in FIG. 1D.
  • an appropriate developer according to the composition of the photosensitive resin composition can be used.
  • the developer is, for example, an alkaline aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide, or an organic amine.
  • the alkaline aqueous solution is, for example, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethyl ammonium hydroxide and water. It contains at least one component selected from the group consisting of lithium oxide.
  • the solvent in the alkaline aqueous solution may be water alone or a mixture of water and a hydrophilic organic solvent such as lower alcohols.
  • the organic amine contains, for example, at least one component selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine.
  • the developer is preferably an alkaline aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide, and particularly preferably an aqueous sodium carbonate solution. In this case, it is possible to improve the work environment and reduce the burden of waste disposal.
  • the coating 4 is cured by heating.
  • the heating conditions are, for example, a heating temperature range of 120 to 200 ° C. and a heating time range of 30 to 120 minutes.
  • the coating film 4 may be further irradiated with ultraviolet rays before or after heating. In this case, photocuring of the film 4 can be further advanced.
  • the interlayer insulating layer 7 made of a cured product of the photosensitive resin composition is provided on the core material 1.
  • the second conductor wiring 8 and the hole plating 9 can be provided on the interlayer insulating layer 7 by a known method such as an additive method.
  • a printed wiring board 11 having a through hole 10 for electrically connecting the first conductor wiring 3 and the second conductor wiring 8 is obtained.
  • the hole plating 9 has a cylindrical shape that covers the inner surface of the hole 6, but the entire inner side of the hole 6 may be filled with the hole plating 9.
  • the core material includes, for example, at least one insulating layer and at least one conductor wiring.
  • a film is formed from the photosensitive resin composition on the surface of the core material where the conductor wiring is provided.
  • Examples of the method for forming the film include a coating method and a dry film method.
  • the coating method and the dry film method the same method as that for forming the interlayer insulating layer can be employed.
  • the film is partially cured by exposure. The exposure method can be the same as the method for forming the interlayer insulating layer.
  • the film is subjected to a development process to remove the unexposed part of the film, whereby the exposed part of the film remains on the core material.
  • the coating on the core material is heated and cured.
  • the developing method and the heating method can be the same as the method for forming the interlayer insulating layer.
  • the film may be further irradiated with ultraviolet rays before or after heating. In this case, photocuring of the film can be further advanced.
  • a solderless resist layer made of a cured product of the photosensitive resin composition is provided on the core material.
  • a printed wiring board provided with the core material provided with an insulating layer and the conductor wiring on it, and the soldering resist layer which partially covers the surface in which the conductor wiring in a core material is provided is obtained.
  • Epoxy compound 1 a bisphenolfluorene type epoxy compound represented by the formula (7) and having an epoxy equivalent of 250 g / eq, wherein R 1 to R 8 in the formula (7) are all hydrogen.
  • Epoxy compound 2 epoxy equivalent 279 g represented by the formula (7), wherein R 1 and R 5 in the formula (7) are all methyl groups, and R 2 to R 4 and R 6 to R 8 are all hydrogen / Eq bisphenolfluorene type epoxy compound.
  • Unsaturated compound B ⁇ -caprolactone-modified dipentaerystol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., product number DPCA-60).
  • Unsaturated compound C Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product number A-DCP).
  • Unsaturated compound D ⁇ -caprolactone-modified dipentaerystol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., product number KAYARAD DPCA-20.
  • Photopolymerization initiator A 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (product number Irgacure TPO, manufactured by BASF).
  • Photopolymerization initiator B 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF, product number Irgacure 184).
  • Photopolymerization initiator C 4,4′-bis (diethylamino) benzophenone
  • Crystalline epoxy resin A 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (high melting type, Melting point 150-158 ° C., epoxy equivalent 99 g / eq).
  • Crystalline epoxy resin B Hydroquinone type crystalline epoxy resin (product name YDC-1312 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., melting point 138 to 145 ° C., epoxy equivalent 176 g / eq).
  • Crystalline epoxy resin C Biphenyl type crystalline epoxy resin (product name YX-4000 manufactured by Mitsubishi Chemical Corporation, melting point 105 ° C., epoxy equivalent 187 g / eq).
  • Crystalline epoxy resin D Diphenyl ether type crystalline epoxy resin (product number YSLV-80DE manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., melting point 80 to 90 ° C., epoxy equivalent 163 g / eq).
  • Crystalline epoxy resin E Bisphenol type crystalline epoxy resin (product name YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., melting point 75 to 85 ° C., 192 g / eq).
  • Amorphous epoxy resin B solution long-chain carbon chain-containing bisphenol A type epoxy resin (manufactured by DIC, product number EPICLON EXA-4816, liquid resin, epoxy equivalent 410 g / eq, structural unit (d1): bisphenol A skeleton, structure A solution of unit (d2): containing a straight-chain hydrocarbon having 6 carbon atoms dissolved in diethylene glycol monoethyl ether acetate at a solid content of 90% (epoxy equivalent in terms of solid content of 90% is 455.56 g / eq) .
  • Amorphous epoxy resin C rubbery core-shell polymer-modified bisphenol F type epoxy resin (manufactured by Kaneka Corporation, product number MX-136, liquid resin, epoxy equivalent 220 g / eq).
  • Amorphous epoxy resin D solution Cresol novolak type epoxy resin, manufactured by DIC, product number EPICLON N-695, softening point 90-100 ° C., epoxy equivalent 214 g / eq dissolved in diethylene glycol monoethyl ether acetate at a solid content of 75% Solution (epoxy equivalent of 75% solid content is 285 g / eq)
  • Amorphous epoxy resin E solution long-chain carbon chain-containing bisphenol A type epoxy resin (manufactured by DIC, product number EPICLON EXA-4822, liquid resin, epoxy equivalent 389 g / eq, structural unit (d1): bisphenol A skeleton, structure Unit (d2): polyethylene glycol, ether oxygen atoms: 4) dissolved
  • Epoxy equivalent in terms of solid content of 80% is 362.5 g / eq.
  • Melamine manufactured by Nissan Chemical Industries, Ltd., fine melamine.
  • Antioxidant A hindered phenol-based antioxidant (manufactured by BASF, product number IRGANOX 1010).
  • Blue pigment phthalocyanine blue.
  • Yellow pigment 1,1 ′-[(6-phenyl-1,3,5-triazine-2,4-diyl) bis (imino)] bis (9,10-anthracenedione).
  • Barium sulfate manufactured by Sakai Chemical Industry Co., Ltd., product number Variace B31.
  • -Talc Product number SG-2000, manufactured by Nippon Talc.
  • Bentonite manufactured by Leox, part number Benton SD-2.
  • Antifoaming agent Product number KS-66 manufactured by Shin-Etsu Silicone Co., Ltd.
  • Surfactant manufactured by DIC, product number MegaFuck F-477.
  • -Rheology control agent manufactured by Big Chemy Japan, product number BYK-430.
  • Solvent A diethylene glycol monoethyl ether acetate.
  • Solvent B methyl ethyl ketone.
  • test pieces were produced as follows.
  • a glass epoxy copper clad laminate (FR-4 type) provided with a 35 ⁇ m thick copper foil was prepared.
  • a comb-shaped electrode having a line width / space width of 50 ⁇ m / 50 ⁇ m was formed as a conductor wiring on this glass epoxy copper clad laminate by a subtractive method, thereby obtaining a core material.
  • a wet paint film was formed by applying the photosensitive resin composition to the entire surface of the core material by screen printing. This wet coating film was heated at 80 ° C. for 40 minutes and preliminarily dried to form a film having a thickness of 25 ⁇ m.
  • Example X17 a test piece was produced as follows.
  • the photosensitive resin composition was applied onto a polyethylene terephthalate film with an applicator and then dried by heating at 95 ° C. for 25 minutes, thereby forming a dry film having a thickness of 25 ⁇ m on the film. Further, a dry film was laminated by heating with a vacuum laminator over the entire surface of the same core material as in Examples X1 to X16, Examples X18 to X22, and Comparative Examples X1 to X11. The conditions for heat lamination are 0.5 MPa, 80 ° C., and 1 minute. As a result, a 25 ⁇ m-thick film made of a dry film was formed on the core material. The film was exposed, developed and irradiated with ultraviolet light under the same conditions as described above.
  • the film made from a polyethylene terephthalate was peeled from the dry film (coating) after exposure and before development.
  • cured material of the photosensitive resin composition (it can also be said to be hardened
  • a test piece was obtained.
  • test pieces were produced as follows.
  • Core materials were obtained in the same manner as in Examples X1 to X22 and Comparative Examples X1 to X11.
  • the conductor layer was roughened by dissolving and removing the surface layer portion of the core member having a thickness of about 1 ⁇ m with a product number CZ-8100 manufactured by MEC Co., Ltd. Thereafter, in the same manner as in Examples X1 to X22 and Comparative Examples X1 to X11, a layer made of a cured product of the photosensitive resin composition was formed on the core material. As a result, a test piece was obtained.
  • test pieces were produced as follows.
  • a dry film was formed in the same manner as in Example X17. Further, a dry film was laminated by heating with a vacuum laminator over the entire surface of the same core material as in Examples Y1 to Y18 and Comparative Examples Y1 to Y5, Examples Z1 to Z20 and Comparative Examples Z1 to Z7. The conditions for heating lamination are the same as in Example X17. Thereafter, the same process as in Example X17 was performed to obtain a test piece.
  • Example X17, Example Y19, and Example Z21 a wet coating film was obtained by applying a photosensitive resin composition to the entire surface of the printed wiring board by screen printing. Formed. The wet coating film was heated at 80 ° C. for 40 minutes and 60 minutes to form a 25 ⁇ m thick film. This film was developed without exposure. In the development process, a 1% Na 2 CO 3 aqueous solution at 30 ° C. was jetted for 90 seconds at a jet pressure of 0.2 MPa, and then pure water was jetted for 90 seconds at a jet pressure of 0.2 MPa. The printed wiring board after the treatment was observed, and the result was evaluated as follows.
  • A The film was completely removed regardless of whether the heating time of the wet coating film was 40 minutes or 60 minutes.
  • B When the heating time of the wet coating film was 40 minutes, all the coating film was removed, but at 60 minutes, a part of the coating film remained on the printed wiring board.
  • C A part of the film remained on the printed wiring board regardless of whether the heating time of the wet coating film was 40 minutes or 60 minutes.
  • Example X17, Example Y19, and Example Z21 since the membrane
  • Example X17, Example Y19, and Example Z21 development was possible without problems in the development process after exposure.
  • A No abnormality was observed in the appearance of the layer made of the cured product and the metal layer, and peeling of the layer made of the cured product by the cellophane adhesive tape peeling test did not occur.
  • B Although discoloration was recognized in the layer which consists of hardened
  • C Lifting of the layer made of the cured product was observed, and peeling of the layer made of the cured product by the cellophane adhesive tape peeling test occurred.
  • PCT pressure cooker test
  • the test pieces of Examples X1 to X22, Comparative Examples X1 to X11, Examples Y1 to Y19, Comparative Examples Y1 to Y5, Examples Z1 to Z21, and Comparative Examples Z1 to Z7 were 100 in an environment of 121 ° C. and 100% RH.
  • the appearance of the cured layer was evaluated according to the following evaluation criteria. A: No abnormality was found in the layer made of the cured product.
  • C A large discoloration was observed in the layer made of the cured product, and partial swelling occurred.
  • the photosensitive resin composition according to the first aspect is A carboxyl group-containing resin (A); An unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule; A photopolymerization initiator (C); An epoxy compound (D); Containing
  • the carboxyl group-containing resin (A) is a carboxyl group-containing resin (A1) that is a reaction product of an intermediate that is a reaction product of an epoxy compound (a1) and an unsaturated group-containing carboxylic acid (a2) and an acid anhydride.
  • the epoxy compound (a1) has a bisphenolfluorene skeleton represented by the above formula (1).
  • R 1 to R 8 are each independently hydrogen, alkyl having 1 to 5 carbon atoms.
  • a group or halogen The epoxy compound (D) contains a crystalline epoxy resin and an amorphous epoxy resin, The total of the equivalents of the epoxy groups of the crystalline epoxy resin and the amorphous epoxy resin with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A) is in the range of 0.7 to 2.5.
  • This photosensitive resin composition contains a carboxyl group-containing resin (A1) because the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton represented by the formula (1) derived from the epoxy compound (a1). High heat resistance and insulation reliability can be imparted to the cured product of the photosensitive resin composition.
  • the epoxy compound (D) contains a crystalline epoxy resin, the developability of the photosensitive resin composition can be improved.
  • the epoxy compound (D) contains only the crystalline epoxy resin, cracks are likely to occur in the cured product of the photosensitive resin composition while the temperature change including the temperature increase and the temperature decrease is repeated.
  • the epoxy compound (D) contains the crystalline epoxy resin and the amorphous epoxy resin at the predetermined ratio, so that the temperature change is repeated, so that the photosensitive resin composition It can be made hard to produce a crack in hardened
  • the equivalent of the epoxy group of the crystalline epoxy resin is within the range of 0.2 to 1.9 with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A). It is preferable that
  • This photosensitive resin composition can improve developability as compared with a resin having an epoxy group equivalent in the crystalline epoxy resin outside the range of 0.2 to 1.9.
  • the crystalline epoxy resin preferably has two epoxy groups in one molecule.
  • This photosensitive resin composition can make it harder to generate cracks in the cured product of the photosensitive resin composition while the temperature change is repeated.
  • the amorphous epoxy resin comprises a bisphenol type structural unit (d1), a linear hydrocarbon structural unit having 4 to 20 carbon atoms, and an ether oxygen atom. It is preferable to contain an epoxy resin (da) having a structural unit (d2) which is at least one of polyalkylene ether structural units of several 3 or more and 20 or less.
  • This photosensitive resin composition can improve the thermal shock resistance of the cured product as compared with the case where no epoxy resin (da) is contained.
  • the amorphous epoxy resin preferably contains an epoxy resin (db) having a novolak structure and a biphenyl skeleton.
  • This photosensitive resin composition is particularly suitable as an insulating material for printed wiring boards that require high reliability such as line insulation and interlayer migration resistance because the electrical insulation performance of the cured product is enhanced.
  • the acid anhydride preferably contains an acid dianhydride.
  • the molecular weight is adjusted by crosslinking the carboxyl group-containing resin (A1) with the acid dianhydride (a3). For this reason, the carboxyl group-containing resin (A1) in which the acid value and the molecular weight are appropriately adjusted is obtained. And the molecular weight and acid value of carboxyl group-containing resin (A1) are easily adjusted by controlling the quantity of acid dianhydride (a3).
  • the acid dianhydride preferably contains 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride.
  • This photosensitive resin composition makes it easy to obtain a film with suppressed tackiness while ensuring good developability, and a cured product with improved insulation reliability and plating resistance.
  • the carboxyl group-containing resin (A1) preferably has a weight average molecular weight in the range of 1,000 to 5,000.
  • the tackiness of the film formed from the photosensitive resin composition is easily suppressed, and the insulation reliability and plating resistance of the cured product formed from the photosensitive resin composition are easily improved.
  • the developability of the resin composition with an alkaline aqueous solution is likely to be improved.
  • the solid content acid value of the carboxyl group-containing resin (A1) is preferably in the range of 60 to 140 mgKOH / g.
  • the developability of the photosensitive resin composition is likely to be improved.
  • the acid anhydride preferably contains 1,2,3,6-tetrahydrophthalic anhydride.
  • the tackiness of the film formed from the photosensitive resin composition is easily suppressed and the insulation reliability and plating resistance of the cured product formed from the photosensitive resin composition are easily improved.
  • the dry film according to the eleventh aspect is a dried product of the photosensitive resin composition.
  • the dry film contains a carboxyl group-containing resin having a bisphenolfluorene skeleton, it has excellent developability, and cracks are hardly generated while the cured product is repeatedly changed in temperature.
  • a printed wiring board includes a solder resist layer containing a cured product of the photosensitive resin composition.
  • a printed wiring board according to a thirteenth aspect includes an interlayer insulating layer containing a cured product of the photosensitive resin composition.
  • the method for producing a photosensitive resin composition according to the fourteenth aspect is represented by the above formula (1), wherein R 1 to R 8 are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms.
  • R 1 to R 8 are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms.
  • an epoxy compound (a1) having a bisphenolfluorene skeleton that is a halogen is reacted with an unsaturated group-containing carboxylic acid (a2), and an intermediate obtained thereby is reacted with an acid anhydride to produce a carboxyl.
  • the epoxy compound (D) contains a crystalline epoxy resin and an amorphous epoxy resin, and the carboxy
  • the total of the equivalents of the epoxy groups contained in the crystalline epoxy resin and the amorphous epoxy resin with respect to 1 equivalent of the carboxyl group contained in the group-containing resin (A) is within the range of 0.7 to 2.5. It is characterized by being.
  • the carboxyl group-containing resin (A1) has a bisphenolfluorene skeleton represented by the formula (1) derived from the epoxy compound (a1). High heat resistance and insulation reliability can be imparted to the cured product of the photosensitive resin composition containing A1).
  • the epoxy compound (D) contains a crystalline epoxy resin, the developability of the photosensitive resin composition can be improved.
  • the epoxy compound (D) contains only the crystalline epoxy resin, cracks are likely to occur in the cured product of the photosensitive resin composition while the temperature change including the temperature increase and the temperature decrease is repeated.
  • the epoxy compound (D) contains the crystalline epoxy resin and the amorphous epoxy resin at the predetermined ratio, so that the temperature change is repeated, so that the photosensitive resin composition It can be made hard to produce a crack in hardened

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Abstract

L'objet de la présente invention est d'obtenir une composition de résine photosensible présentant une excellente aptitude au développement, même si elle contient une résine contenant un groupe carboxyle et ayant un squelette de fluorène de bisphénol, et d'obtenir un produit durci de la composition de résine photosensible qui soit moins susceptible de se fissurer en cas de changements de température répétés. Une composition de résine photosensible de la présente invention contient une résine contenant un groupe carboxyle (A) ; un composé insaturé, un initiateur de photopolymérisation et un composé époxy. La résine contenant un groupe carboxyle (A) contient une résine contenant un groupe carboxyle (A1) qui est un produit de réaction d'un anhydride d'acide et d'un intermédiaire qui est un produit de réaction d'un acide carboxylique contenant un groupe insaturé et d'un composé époxy ayant un squelette de fluorène de bisphénol représenté par la formule (1). Le composé époxy contient une résine époxy cristalline et une résine époxy amorphe.
PCT/JP2016/000429 2015-11-02 2016-01-28 Composition de résine photosensible, film sec et carte de circuits imprimés WO2017077662A1 (fr)

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JP2015215709A JP6140246B2 (ja) 2015-11-02 2015-11-02 感光性樹脂組成物、ドライフィルム、プリント配線板、及び感光性樹脂組成物の製造方法
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WO2022124296A1 (fr) * 2020-12-10 2022-06-16 三菱ケミカル株式会社 Composition de résine photosensible, produit durci, masque noir et dispositif d'affichage d'image

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WO2018225441A1 (fr) * 2017-06-09 2018-12-13 互応化学工業株式会社 Composition de résine photosensible, film sec, et carte de circuit imprimé
KR102312785B1 (ko) * 2017-08-10 2021-10-14 동우 화인켐 주식회사 광중합성 불포화 수지, 이를 포함하는 감광성 수지 조성물 및 이로부터 형성되는 차광성 스페이서와 액정 디스플레이 장치
JP7091463B2 (ja) * 2018-09-28 2022-06-27 富士フイルム株式会社 転写材料、積層体、及び、積層体の製造方法
JP7202282B2 (ja) * 2019-12-16 2023-01-11 株式会社タムラ製作所 感光性樹脂組成物及び感光性樹脂組成物を有するドライフィルム
CN112940560B (zh) * 2021-02-01 2022-11-29 深圳市容大感光科技股份有限公司 感光阻焊油墨组合物、其用途以及含有其的线路板
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